Cyclic and acyclic examples of 2-aza-1,3-dienes, a new functional group, and a cyclic example of a 1-aza-1,3-diene, a little studied functional group, have been synthesized, and their essential chemistry, emphasizing cycloaddition reaction, is under investigation. These conjugated systems have good potential as intermediates for the preparation of a wide variety of heterocyclic systems and examples of the 1-azabicyclo(-2.2.1.)hiptane, 1-azatricyclo(5.2.1.0(2,6))decane, 1-azatetracyclo(6.2.1.1(3,6).0(2,7)dodecane, and the isoquinoline series have been prepared. Also, present techniques appear adaptable for the synthesis of azapolyenes and examples of the 3-aza-1,3,5-hexatriene system have been prepared.